JPH0196644A - Direct positive type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the good image quality of the title material having sufficiently high max. density and sufficiently low min. density by providing a photographic sensitive layer which contains at least two kinds of silver halide emulsions having different means particle sizes respectively, and is incorporated with a specified compd. at the time of preparing said emulsion, on a supporting body. CONSTITUTION:At least one layer of the photographic sensitive layers which contain at least two kinds of the silver halide emulsions having the different mean particle sizes respectively, and are incorporated with the compd. shown by formula I at the time of preparing said emulsion, is provided on the supporting body. In formula I, X is H atom or NH2 group, Y is OH or NH2 group, etc. The material contains at least one layer of the photographic sensitive layers contg. at least two kinds of the different mean particle sizes respectively. Said layer is constituted of the emulsion formed by mixing >=2 kinds of the silver halide emulsions having the different kinds of the mean particle sizes respectively. Thus, the good image quality of the material having the sufficiently high max. density and the sufficiently low min. density, can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive type silver halide photographic light-sensitive material. In particular, the present invention has a sufficiently high maximum density, a sufficiently low minimum density, good image quality, wide gradation, and direct positive silver halide photography that can be processed stably against fluctuations in processing conditions. It's about materials.

[Foreground of invention]

Although relatively high sensitivity can be obtained as an emulsion used in direct positive silver halide photographic materials,
There are disadvantages that the maximum density Dmax of the direct positive image is low and the minimum density Dmin (fog) of the background part of the image is high.

As described above, the degree of fog and image density varies depending on the type of silver halide emulsion, manufacturing conditions, storage conditions after manufacturing, development processing conditions, etc., but processing conditions in particular vary due to various external factors. Significant when

Specific examples of fluctuations due to external factors include: ■ If the fogging process after image exposure changes for some reason; ■ Local non-uniformity of exposure or temporal fluctuations in light source illuminance in full-surface exposure processing, etc. Cases in which: (1) During fogging treatment, there are cases where fluctuations in the concentration of the fogging agent occur due to air oxidation, thermal decomposition, etc. These do not always give a constant fog to the emulsion, and the image density obtained by development tends to vary.

Therefore, as a direct positive silver halide emulsion, the maximum density is sufficiently high, the minimum density is sufficiently low and good image quality can be obtained, and the fog latitude under the allowable optical fog or chemical fog conditions is sufficiently wide. is necessary.

Traditionally, in addition to the above effects, there are fields that require soft gradation and wide exposure latitude, so it is necessary to lower the gamma value (
As a method for obtaining a wide exposure latitude and soft tonality, there is a known method of mixing direct positive silver halide emulsions having different sensitivities, for example, a method of mixing emulsions using a desensitizer. However, it is unfavorable in terms of silver utilization efficiency and image graininess. In order to obtain softer gradation, it is also known to mix silver halide with a larger difference in grain size. However, in this case, silver halides with significantly different average grain sizes coexist, so when developing them, the development speed is different between silver halide with a large grain size and silver halide with a small grain size. There is a large difference in the processing conditions, and stable processing cannot be achieved even with changes in processing conditions.

In addition, direct positive silver halide emulsions with different sensitivities have different fog latitudes, so in a mixed system, the fog latitudes (overlapping portions of the respective fog latitudes) become narrower, and the image density obtained through development processing varies. The disadvantage is that it is easier.

[Purpose of the invention]

The present invention has been made to solve the above problems, and has a sufficiently high maximum density, a sufficiently low minimum density, good image quality, a sufficiently low gamma value, soft gradation, and a wide exposure latitude ( A direct positive silver halide photographic sensitizer that has a sufficiently wide fog latitude (tolerable range of exposure or processing solution during fog development) and can be processed stably against fluctuations in processing conditions. The purpose is to obtain materials.

[Structure and operation of the invention]

The above-mentioned object of the present invention is to provide a direct positive silver halide photographic light-sensitive material that directly produces a positive image by imparting optical fog during development or developing in the presence of a fogging agent after image exposure, which comprises: Having on a support at least one photographic light-sensitive layer containing at least two types of silver halide emulsions having different average grain sizes, each containing a compound represented by the following general formula [I] added at the time of preparing the emulsion. This is achieved using a direct positive type silver halide photographic material with special characteristics.

The above general formula (1) in the present invention represents. However, R1 and R2 will not become H at the same time. ).

The photographic light-sensitive material according to the present invention has at least one photographic light-sensitive layer containing at least two types of silver halide emulsions having different average grain sizes; It can be constructed by containing an emulsion formed by mixing more than one type of silver halide emulsion. In a preferred embodiment of the photosensitive layer, S is the average grain size of the silver halide emulsion with the smallest average grain size, and L is the average grain size of the silver halide emulsion with the largest average grain size.
Preferably S is 0.2 μm to 0.5 μm and L is 0.4
μm to 0.9 μm, more preferably S is 0.2
5 p m -0.45 p m and L is 0.45 p
There is an embodiment in which m-0.85pm.

In the present invention, a compound represented by the general formula CI) is added to at least two types of silver halide emulsions having different average grain sizes at the time of emulsion preparation.

The time of emulsion charging and preparation refers to any time during the growth of silver halide grains. Here, silver halide grains are growing.
It refers to any point in time just before a silver halide grain grows and completes as a grain, and does not include after grain formation. core/
In the case of forming shell-structured particles, the particles may be formed at a time during core formation, after core formation and immediately before shell formation, or during shell formation.

The silver halide grains used in the present invention preferably have a core/shell structure, and the compound of general formula (1) is preferably added during the growth of the silver halide grains, particularly during the formation of the shell. is preferred. The amount of the compound of general formula CI) added is preferably 10 mg/mol Ag to 300
mg 1 mol Ag, more preferably 30 mg/mol Ag ~
150 mg/mol 8 g. In each emulsion, it is desirable that the amount of the compound of general formula (1) added to the emulsion with the smallest average grain size be greater than the amount of the compound of general formula (1) added to the other emulsions.

The light-sensitive material of the present invention has at least one photographic constituent layer containing at least two types of silver halide emulsions having different average grain sizes as described above, and has two or more layers sensitive to substantially the same wavelength. When a light-sensitive layer is formed using a photosensitive layer, the average grain size of the emulsion contained in one of the two or more layers and the silver halide emulsion contained in the other layer (both IN and IN) are different, and this causes the substantial This includes cases in which a layer sensitive to the same wavelength contains 642 or more types of emulsions.

That is, in the present invention, the photosensitive layers sensitive to the same wavelength may be a single layer or a multilayer, and the photographic photosensitive layer as a whole contains at least two types of silver halide emulsions having different average grain sizes. All you have to do is stay there. When the photosensitive layer is a single layer, the layer contains two types of silver halide emulsions with different average grain sizes.When the photosensitive layer is a multilayer, one layer and another layer are combined. Each layer of the multilayer may contain an emulsion mixed with silver halide grains of different grain sizes, and each layer of the multilayer may contain an emulsion containing a single silver halide grain. The photosensitive layer as a whole may contain emulsions having different average grain sizes.A preferred embodiment is when the photosensitive layer is a single layer, in which case manufacturing is easy and processing can be speeded up. However, it may be multi-layered.

The present invention will be explained in more detail below.

First, the compound represented by the general formula [I] used in the direct positive silver halide photographic material of the present invention will be explained.

Represents each layer of cycloalkyl or ester. However, II and R8 will not become H at the same time. ).

Note that the above alkyl group includes substituted ones,
Specifically, for example, there are those substituted with a cyano group and those substituted with a pyridine group. The above-mentioned aryl groups also include substituted ones, and specifically, for example, there are those substituted with a dimethoxy group and those substituted with a carboxyl group.

Specific examples of the alkyl group represented by R1 and R1 include methyl group, ethyl group, n-butyl group, n-hexyl group, etc., and cycloalkyl group includes cyclohex, sil group, etc. Further, specific examples of each layer of aryl include a benzyl group and a phenethyl group. Among these, preferred are a cyclohexyl group as a cycloalkyl group and a benzyl group as an aryl group.

Next, specific examples of the compound represented by the general formula (I) used in the present invention include the following.

General formula (I) (1) These compounds in the present invention can be easily synthesized by known methods or methods analogous thereto.

For example, J, Am, Chem, Soc, 81.396
3-3967 (1959), same magazine 79.2251-2
252 (1957). Moreover, some compounds are commercially available as chemical reagents.

Among the compounds represented by the general formula [I], those having an excellent effect of improving positive images, which is the object of the present invention, include (
Compounds represented by 1-8) and (1-111) are preferred.

Some of these compounds in the present invention are I! contained in gelatin. Although it is known as an acid component, its content is far less than the amount sufficient to exhibit the effects of the present invention, so its influence is completely out of the question.

',y,:,,IH Next, the preparation of the silver halide emulsion used in the present invention will be described. Two or more emulsions are prepared as follows so as to have a desired average grain size, and the emulsions are mixed (can be used in separate layers in the same photosensitive layer).

That is, the silver halide grains used in the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created.

The method of creating and growing the seed particles may be the same or different. A silver halide emulsion containing the silver halide grains may be prepared by simultaneously mixing halide ions and silver ions, or by mixing one of them in a solution in which the other is present.

Also, while considering the critical growth rate of silver halide crystals,
pH and pA of halide ion and silver ion mixing pot
It may also be produced by sequentially and simultaneously adding them while controlling the amount of g. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

The halogen composition of the particles can also be changed using a compaction method after growth. The silver halide emulsion obtained as described above may have any grain size distribution. Therefore, an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. A mixture of emulsions may be used. Preferably, a monodisperse emulsion is used. Here, the monodispersity of a monodisperse emulsion refers to an emulsion in which the coefficient of variation in the grain size distribution of silver halide grains contained in the emulsion is 22% or less, preferably 15% or less.

Here, the particle size of particles for obtaining the above particle size distribution refers to the diameter in the case of spherical particles, and in the case of other shapes, the diameter of a circle with an area equal to the projected area of the particles. This can be measured by electron microscopy.

Next, a preferred method for producing silver halide grains used in the present invention will be described.

The silver halide grains used in the present invention may be composed of at least two types of layers, that is, at least two types of layers having different halogen compositions, and the outermost shell layer is at least a part of the inner core layer. It may be sufficient to just cover it. It is preferable to adopt a so-called core/shell structure in which the inner core layer forms a core and the outer shell layer covers the core as a shell, and a structure in which the first layer covers a part of the second layer may be adopted.

The silver halide grains according to the present invention may be composed of three or more types of layers. For example, the first core, which is the most central
Silver halide grains may have a three-layer structure consisting of a layer, an inner core layer covering the layer, and an outer shell layer further covering the inner core layer. Hereinafter, in order to simplify the explanation, we will take a particle with a two-layer structure, and refer to the outermost first layer as the outer shell layer,
The second layer adjacent to it will be explained as the inner core layer, but
The silver halide grains of the present invention are not limited to grains with a two-layer structure.

The inner core layer of the silver halide grain preferably contains less silver chloride than the silver chloride contained in the outer shell layer.

The inner core layer preferably mainly consists of silver bromide and may further contain silver chloride and/or silver iodobromide.The shape of the silver halide grains forming the inner core layer can be any shape. For example, it may be a cube, a regular octahedron, a dodecahedron, a tetradecahedron, or a mixture thereof, or it may be a spherical, tabular, irregularly shaped particle, or an appropriate mixture of these. In practicing the present invention, the average particle size and particle size distribution of the silver halide grains constituting the inner core layer can be varied widely depending on the desired photographic performance, but it is more preferable that the particle size distribution is narrow. Specifically, it is preferable that 90% by weight of the silver halide grains constituting the inner core layer is 40% or more away from the average grain diameter, and more preferably, the silver halide grains have diameters that are no more than 30% apart from the average grain diameter.

That is, the silver halide grains constituting the inner core layer are preferably substantially monodisperse.

Here, the term "silver halide grains with a monodisperse inner core layer" means that the weight of the silver halide grains included in the grain size range of ±20% around the average grain size Y in the silver halide grains constituting the inner core layer is It is 60% or more of the total silver halide weight, preferably 70% or more, particularly preferably 80% or more.

Here, the average grain weight 7 is the grain size r! It means the particle size ri at which the product n1Xri' of the frequency n of particles having the following value and riz is the maximum (3 significant figures, the minimum number of digits is 4 to 5).

In addition, the grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than spherical, the diameter when the projected image is converted into a circular image with the same area. It is.

The particle size can be obtained, for example, by magnifying the particle 10,000 to 50,000 times with an electron microscope and projecting it, and actually measuring the particle diameter or area at the time of projection on the print (the number of particles measured is (Assume there are more than 1000 items indiscriminately.)

Examples of the method for producing the monodisperse core emulsion include, for example, Japanese Patent Publication No. 48-36890, Japanese Patent Application Laid-Open No. 54-48520,
The double jet method disclosed in various publications such as No. 54-65521 can be used. In addition, JP-A-54-158
A premix method described in Japanese Patent No. 220 and the like can also be used.

The inner core layer preferably has few lattice defects and is disclosed, for example, in US Pat. No. 2,592,250.

Emulsions produced by conversion methods are not suitable as inner core layers. pH and pAg during production by the above double jet method
Particles produced while controlling the lattice defects have fewer lattice defects and are preferable as the inner core layer.

The inner core layer can be prepared in the presence of a silver halide solvent. Thioethers shown in U.S. Patent No. 3,574,628, thiourea derivatives shown in JP-A-55-77737, imidazoles shown in JP-A-54-100717, etc. can be used. .

In a preferred embodiment of the present invention, ammonia is preferably used as the silver halide solvent.

The outer shell layer preferably covers 50% or more of the surface area of the grains constituting the inner core layer, and may contain silver bromide or silver iodide within a range that does not adversely affect photographic performance. . A portion of the outer shell layer can be converted into silver bromide or silver iodide using a trace amount of water-soluble bromide or iodide.

The outer shell layer can completely cover the inner core layer or can selectively cover a part of the inner core layer, but preferably covers 50% or more of the surface area of the particles constituting the inner core layer. is preferred. More preferably, the inner core layer is completely covered.

As a method for forming the outer shell layer, the above-mentioned double jet method, premix method, etc. can be used. It is also possible to form the inner core layer by mixing fine grains of silver halide with an emulsion containing grains constituting the inner core layer and performing Ostwald ripening.

In practicing the present invention, the inner core layer of the silver halide grains is chemically sensitized, doped with metal ions, or both, or not at all. It may be something.

As the chemical sensitization, sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and a combination of these sensitization methods can be employed. As the sulfur aggravating agent, thiosulfur salts, thioureas, thiazoles, rhodanines, and other compounds can be used.

Such methods are described, for example, in U.S. Pat. No. 1,574,944.
No. 1,623.499, No. 2.410.689, No. 3,656.955, etc.

The inner core layer of the silver halide grains used in carrying out the present invention is, for example, US Pat. No. 2,399.083;
As described in No. 597.856, No. 2,642.361, etc., sensitization can be carried out with a water-soluble gold compound or with a reduction sensitizer.

Such methods are described, for example, in U.S. Pat.
．． No. 850, No. 2,518.698, No. 2.983.
Reference can be made to the description in No. 610 and the like.

Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. Such methods are described, for example, in U.S. Pat.
Reference may be made to the descriptions in No. 8.060 and British Patent No. 618.061.

Additionally, the inner core layer of the silver halide grains can be doped with metal ions. To dope the inner core layer with metal ions, the metal ions can be added as water-soluble salts, for example, during any process of forming particles of the inner core layer. Preferred specific examples of metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions are preferably used in concentrations of 1X10-'' to 1X10-' mole per mole of silver.

However, those used as the inner core layer of silver halide grains are
The material may not be subjected to the above-mentioned chemical sensitization treatment or metal ion doping.

In this case, it is thought that photosensitive centers are generated by forming crystal strain at the interface between the inner core layer and the outer shell layer during the process of covering the particles in the inner core layer with the outer shell layer. Reference may be made to the descriptions in US Pat. No. 3,935.014 and US Pat. No. 3,957.488.

The silver halide emulsion used in the present invention can be chemically sensitized by a conventional method at any stage of production. Furthermore, the silver halide grains of the present invention can store polyvalent metal ions inside the grains. Preferred specific examples of polyvalent metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, platinum, osmium, and rhodium.

In the silver halide grains according to the present invention, it is preferable that the grain surface is not chemically sensitized, or even if it is sensitized, it is only to a small extent.

In the direct positive silver halide photographic material of the present invention, internal latent image type silver halide grains whose surfaces are not fogged in advance can be used. Here, the meaning that the surface of the internal latent image type silver halide grains is not fogged in advance means that such an emulsion is coated on a transparent film support with 35 mgAg/
It means that the density obtained when a test piece coated to give ci is developed with the following surface developer A at 20°C for 10 minutes without exposure to light does not exceed 0.6, preferably 0.4.

Surface developer A Metol 2.58 1-Ascorbic acid 10 g NaBOz ・
4Hz 35gKBr
Add 1g water
1N Furthermore, the emulsion containing silver halide grains according to the present invention provides sufficient density when the test piece prepared as described above is exposed and then developed with internal developer B having the following formulation. .

Internal developer B Metol 2g Sodium sulfite (anhydrous) 90 g Hydroquinone 8g Soda carbonate (-hydrate) 52.5 gKBr
5 gKl
11. To be more specific, a portion of the test piece was mixed with about 1.0 g of water.
When exposed to a light intensity scale for a defined time up to seconds and developed in internal developer B for 10 minutes at 20°C, another part of the specimen exposed under the same conditions was exposed in surface developer A. The image obtained when developing for 10 minutes at 20°C
The maximum concentration is at least 5 times, preferably at least 10 times greater than that of the present invention.

Silver halide emulsions can be optically sensitized using commonly used sensitizing dyes. Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative-working silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, see Research Disclosure.
e) Reference may be made to Na 15162 and & 17643.

When directly obtaining a positive image using the direct positive silver halide photographic light-sensitive material of the present invention, after image exposure (so-called photography, in which light is applied to the light-sensitive material to form an image) is carried out in the usual manner. By surface developing this, a positive image can be easily obtained directly. That is, the main process for directly forming a positive image is to process a photographic material having an internal latent image type silver halide emulsion layer, after image exposure, to generate fog nuclei by chemical or photochemical action (hereinafter referred to as capri processing). It consists of performing surface development after applying a capri treatment and/or while applying a capri treatment.

Here, the fogging treatment can be carried out by exposing the entire surface to light or using a compound (hereinafter referred to as a fogging agent) that generates fogging nuclei.

For example, full-surface exposure is performed by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then exposing the entire surface uniformly to light. The light source used here may be any light within the sensitive wavelength range of the photographic light-sensitive material, and it may be a short-term exposure to high-intensity light such as a flash light, or a long-term exposure to weak light. Furthermore, the overall exposure time can be varied over a wide range depending on the photographic material, processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image.

Further, it is most preferable that the exposure amount for full-surface exposure is within a certain range in combination with the photosensitive material.

A wide variety of compounds can be used as the capri agent used in the present invention, and the capri agent only needs to be present during the development process. (preferably in the silver oxide emulsion layer), or may be contained in the developer or the processing solution prior to development. The amount used can be varied over a wide range depending on the purpose, and the preferred amount is 1 to 1,500 μm per mole of silver halide, preferably 10 to 1 μm per mole of silver halide.
It is 000■. Further, when added to a processing solution such as a developer, the preferred amount is 0.01 to 5 g/l, particularly preferably 0.05 to 1 g/l.

Examples of the fogging agent used in the present invention include those described in US Pat.
563.785, hydrazines described in 2,588,982, or U.S. Pat. No. 3,227.5
Hydrazide or hydrazine compounds described in US Pat. No. 3.615.615 and US Pat. No. 3.718.47
No. 0, No. 3.719°494, No. 3.734.738
No. 4 and heterocycle No. 4 described in No. 3,759,901
Further examples include compounds having an adsorption group on the surface of silver halide, such as acylhydrazinophenylthiourea described in US Pat. No. 4,030,925. Further, these fogging agents can also be used in combination.

For example, research disclosure (Reseac)
h Dis-closure) 11h15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type capri agent.

As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, and they can also be used in combination.

Specific examples of useful capri agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2-(4-acetamidophenyl)hydrazine, 1 -Methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1
- Hydrazine compounds such as methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine: 3-(2-formylethyl)-2-methylbenzothiazolium bromide, 3-(2-formylethyl) )-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)
-2-benzylbenzoselenazolium bromide, 3-
(2-acetylethyl)-2-benzyl-5-phenyl-benzoxacilium bromide, 2-methyl-3-
(3-(phenylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-(3-(p-tolylhydrazino)propyl)benzothiazolium bromide, 2-methyl-3-(3-(p- Sulfophenylhydrazono)propyl benzothiazolium bromide,
2-Methyl-3-(3-(p-sulfophenylhydrazono)pentyl]benzothiazolium iodide, 1.2
-dihydro-3-methyl-4-phenylpyrido (2,1
-b) Benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrid [2,1b]-
5-phenylbenzoxazolium bromide, 4.4
'-ethylenebis(1,2-dihydro-3-methylpyrido[2,1-b)benzothiazolium bromide), 1
．． 2-dihydro-3-methyl-4-phenylpyrido (2
, 1-b) N-substituted quaternary cycloammonium salts such as benzoselenazolium bromide; 5-[1-ethylnaphtho(1,2-b)thiazolin-2-ylideneethylidene)-1-(2-phenyl Carbazoyl)methyl-3-(
4-sulfamoylphenyl)-2-thiohydantoin, 5-(3-ethyl-2-penzothiazolinylidene)-
3-(4-(2-formylhydrazino)phenylchorodane, 1-(4-(2-formylhydrazino)phenyl)3-phenylthiourea, 1.3-bis(4-(2-formylhydrazino)phenyl)
-formylhydrazino) phenylcothiourea and the like. - After image exposure, the photographic light-sensitive material of the present invention forms a positive image directly by exposing the entire surface to light or developing it in the presence of a capriagent. Although any development method can be employed as the development method for the photographic material according to the present invention, a surface development method is preferable. This surface development processing method means processing with a developer substantially free of silver halide solution.

Developers that can be used in the developer used for developing the photographic light-sensitive material according to the present invention include common silver halide developers, such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, Contains ascorbic acid, its derivatives, reductones, phenylenediamines, etc., or mixtures thereof.

Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, N,N-diethyl-p-phenylenediamine, diethylamino-0-toluidine, '4-amino-3-methyl-N-ethyl-N
-(β-methanesulfonamidoethyl)aniline, 4
-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline and the like. These developers may be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution.

The developer used in the present invention may further contain certain antifoggants and development inhibitors, or these developer additives may optionally be incorporated into the constituent layers of the photographic material. .

Commonly useful antifoggants include benzotriazoles such as 5-methylbenzotriazole, benzoxazoles, benzothiazoles, benzoxazoles,
- Heterocyclic thiones such as -phenyl-5-mercaptotetrazole, aromatic and aliphatic mercapto compound breastplates. Further, a development accelerator such as a polyalkylene offside derivative or a quaternary ammonium salt compound can also be contained in the developer.

Generally, after developing a silver halide photographic light-sensitive material, a fixing process is performed using a processing solution containing a silver halide solvent to remove unnecessary silver halide, or when a color image is obtained by the developing process. In order to remove unnecessary silver halide and metallic silver formed by development, a bleach-fixing process is usually performed using a processing solution containing a silver halide solvent and an oxidizing agent. In order to speed up processing, when a photographic material is used that undergoes direct fixing or bleach-fixing after development without washing with water or stopping with an acid bath, the minimum density of the image can be kept low; Good quality images can be obtained.

Various photographic additives may optionally be added to the emulsion containing silver halide grains according to the present invention.

Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid. Suitable are water-dispersible particulate polymeric substances obtained by emulsion polymerization such as copolymers with acrylic acid, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc.
Coating aids include, for example, saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, I)H preparation agents, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, It is optional to use a developing speed adjustment agent, a matting agent, etc.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer and a filter layer, if necessary, to obtain an internal latent image type silver halide photographic light-sensitive material.

It is useful to apply the present invention to color photographic light-sensitive materials; in this case, it is preferable to include cyan, magenta, and yellow dye image-forming couplers in the silver halide emulsion; the couplers are commonly used couplers. can be used.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent browning of dye images due to short-wavelength actinic rays, especially Tinuvin PS, Tinuvin 320, Tinuvin 326 , 327, and 328 (all manufactured by Ciba Geigy) are useful alone or in combination.

Any support can be used, but typical supports include polyethylene terephthalate film, polycarbonate film, and
Includes polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc.

In addition to gelatin, an appropriate gelatin derivative may be used as a protective colloid or binder in the emulsion containing silver halide grains according to the present invention, depending on the purpose. Examples of suitable gelatin derivatives include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders can be included depending on the purpose. In addition to gelatin, these complex binders include colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl Contains 19
% to 20% hydrolyzed cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylamino acetate copolymers. , polyvinyl alcohol, polyvinylpyridone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc. can be added to the constituent layers of photographic materials such as emulsion layers, intermediate layers, protective layers, filter layers, backing layers, etc., depending on the purpose.Additionally, to the above-mentioned wood-philic binder, suitable plasticizers, It can contain a lubricant or the like.

Further, the constituent layers of the photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent. Examples of these hardening agents include chromium salts, zirconiums, aldehydes such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. .

In addition, the photographic light-sensitive material according to the present invention may have a large number of various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer on a support. is possible.

〔Example) Next, the present invention will be specifically explained with reference to Examples.

However, it goes without saying that the embodiments of the present invention are not limited to the embodiments illustrated below.

Example-1 (Preparation of emulsions A, B, C, D, E, F, G) Equimolar aqueous silver nitrate solution and potassium bromide aqueous solution were mixed at a constant pH (9,
0) and P A g (8,3) by adding them simultaneously using the double jet method, the average particle size was 0.
．． 13 μm (emulsion: A), 0.14 μm (emulsion:
B), 0.21 μm (emulsion: C), 0.
32 μm (emulsion: D), 0.42 μm (emulsion:
E), 0.6 μm (emulsion: F), 0.6
A cubic silver bromide emulsion of 3am (emulsion 2G) was obtained. Each particle size difference was obtained by adjusting the temperature and addition time.

Using these emulsions A, B, C, D, E, F, and G as core particles, a core/shell emulsion as shown below was obtained.

(Preparation of emulsions A and ~A1.) Using emulsion A' as a core particle, a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide (molar ratio of NaCl:KBr=40:60) were added for about 5 minutes. By adding at the same time, the average particle size is 0.18μ.
m cubic core/shell type emulsions A1 to A1B were obtained. However, one minute after starting the addition of the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution, the additive compounds were added in amounts calculated per mole of silver as shown in Table 1. Note that the additive compound here includes the comparative compound (X-1)
, (X-2) and (X-3), and one of the exemplified compounds (1-5), (1-8) and (1-11) of general formula (1)
Seeds are used.

(Preparation of emulsions B and ~Bl&) Emulsion B was used as a core particle, and a mixed aqueous solution of silver nitrate aqueous solution, sodium chloride and potassium bromide (in a molar ratio of N
aC1:KBr=40:60) over a period of about 6 minutes to form cubic core/shell type emulsions 81-B1. I got it. however,
One minute after starting the addition of the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution, the additive compounds were added as shown in Table 2! ! The amount was added in an amount calculated per mol. Note that the additive compounds include comparative compound (X-1), (
X-2) and (X-3), and one of the exemplified compounds (1-5), (1-8) and (I-11) of general formula (1) are used.

(Preparation of Emulsions 01 to C19) Emulsion C was used as a core particle, and a mixed aqueous solution of silver nitrate aqueous solution, sodium chloride and potassium bromide (in a molar ratio of N
aC1: KBr=40:60) over a period of about 8 minutes to obtain a cubic core/shell type emulsion CI"'C19 with an average grain size of 0.3 μm. However, silver nitrate aqueous solution and sodium chloride/bromide One minute after the start of addition of the potassium mixed aqueous solution, the additive compound was added in an amount calculated per mole of silver as shown in Table 3.In addition, Cf9 was added to the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution. The additive compound was added immediately before adding the comparative compound (X-1).
).

(X-2) and (X-3], and one of the exemplified compounds (1-5), (1-8), and (1-11) of general formula (1) are used.

(Preparation of emulsion, ~DIS) Using the emulsion as a core particle, further add a silver nitrate aqueous solution, a mixed aqueous solution of sodium chloride and potassium bromide (in a molar ratio of N
aCf: KBr-40: 60) over a period of about 12 minutes to reduce the average particle size to 0.45μ.
A cubic core/shell type emulsion DI-wDII of m was obtained. However, one minute after starting the addition of the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution, the additive compounds were added in amounts calculated per mole of silver, as shown in Table 4. Note that the additive compound here includes a comparative compound (X-1
), (X-2) and (X-3), and one of the exemplified compounds (1-5), (I-8) and (1-11) of general formula (1) is used.

(Preparation of emulsion El-Etw) Emulsion E was used as a core particle, and a mixed aqueous solution of silver nitrate aqueous solution, sodium chloride and potassium bromide (in molar ratio M
ace: &Br=40:60) over a period of approximately 16 minutes, the average particle size was reduced to 0.6μ.
A cubic core/shell type emulsion E, ~E19 of m was obtained. However, one minute after starting the addition of the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution, all of the added compounds were added in terms of 111 moles as shown in Table 5. Further, in E19, the additive compound was added immediately before adding the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution. Note that the additive compound here includes a comparative compound (X-
13° (X-2) and (X-3), and one of the exemplified compounds (1-5), (1-8) and (1-11) of general formula (1) are used.

(Preparation of emulsions F1 to l''Ill) Using emulsion F as a core particle, a mixed aqueous solution of silver nitrate aqueous solution, sodium chloride and potassium bromide (in a molar ratio of N
aC1:KBr=40:60) was added simultaneously over about 24 minutes to reduce the average particle size to 0.85μ.
m cubic core/shell type emulsions F1 to F'+s were obtained.

However, one minute after starting the addition of the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution, all of the added compounds were added in terms of per mole of silver as shown in Table 6. Note that the additive compounds here include comparative compound (X-1),
(X-2) and (X-3), and one of the exemplified compounds (1-5), (1-8) and (1-11) of the general formula (Ill)
Seeds are used.

(Preparation of emulsions G and ~G1.) Using emulsion G as a core particle, a mixed aqueous solution of silver nitrate aqueous solution, sodium chloride and potassium bromide (in a molar ratio of N
aC1: KBr=40:60) over a period of about 36 minutes to form cubic core/shell type emulsions 01 to G1. with an average grain size of 0.9 μm. I got it. However, one minute after starting the addition of the silver nitrate aqueous solution and the sodium chloride/potassium bromide mixed aqueous solution, all of the added compounds were added in terms of per mole of silver as shown in Table 7. Note that the additive compounds include comparative compounds (X-1) and (X
-2) and (X-3) and the exemplified compound of general formula (1) (
One type out of I-5), (1-8) and (1-11) is used.

A sensitizing dye (Z
-1), then add a protectant containing surfactant (S-2), dibutyl phthalate, ethyl acetate, 2.5-dioctylhydroquinone, surfactant (S-1), and magenta coupler (MC-1). The dispersed coupler solution was added. Gelatin was added to this, and a hardening agent ()fA-
1) was added and coated on a resin-coated paper support so that the coated silver amount was 4 cm/100 c1a, and dried.

These samples were wedge-exposed through a yellow filter and subjected to the following development treatments.

However, for the fog exposure in processing step [2] shown below, the illuminance is 0.125 lux, 0.17 lux, 0.2
50 Lux, 0.354 Lux, 0.500 Lux, 0.70 Lux, 1.00 Lux,
1.41 Lux, 2.00 Lux, 2.83 Lux, 4.00 Lux, 5.66 Lux,
It was changed to 8.00 lux, 11.3 lux, and 16.0 lux.

Processing process (processing temperature and processing time) [1] Immersion (color developer) 38℃ 8 seconds [2] Fog exposure 10 seconds [3] Color development
38°C 2 minutes [4] Bleach fixing 35°C 60 seconds [5] Stabilization treatment 25-30″01 minute 30 seconds [
6] Drying at 75-80°C for 1 minute Processing solution composition (color developer) Benzyl alcohol 10 d Ethylene glycol 15 m2 Potassium sulfite
2.0g potassium bromide
1.5g sodium chloride
0.2g potassium carbonate 3
0.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-
Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1, 0
g Potassium hydroxide 2.0g Add water to make a total of 11N, and adjust the pH to 10.20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid diammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 1001n1 Ammonium sulfite (4
0% solution) 27.5mff1 Adjust to pi-17.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 11.
shall be.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g l-hydroxyethylidene-1,1'-diphosphonic acid 2.5 g bismuth chloride 0.2 g magnesium chloride 0. 1g ammonium hydroxide (2
8% aqueous solution) 2.0g sodium nitrilotriacetate Add 1.0g water to bring the total volume to 11, and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

Note that the stabilization treatment was performed using a countercurrent method with a two-tank configuration as described above.

Sensitizing dye (Z-1) Surfactant (S-1) (S-2) gHs ■ CHz COOCl1z CH (CL) + CH
Hardener (HA-1) Shinki Magenta Coupler (MC-1) Reflection density was measured using green light for each sample after the treatment.

Note that Capri exposure latitude is defined as follows.

When each sample is processed with different Capri illuminance, if the Capri illuminance is L+ or more, the maximum density is 1.6 or more, and if the Capri illuminance is Lx or less, the minimum density is 0.2 or less, then the Capri exposure latitude is .

Tables 1 to 7 show the measurement results of Capri exposure latitude, maximum density, and minimum density. Here, a single emulsion containing one of the exemplary compounds (1-5, 1-8, l-11) of general formula (1) and the comparative compounds (X-2, X-3゜x-4) was used. This is the result for the case.

As is clear from the results in Tables 1 to 7, in the single emulsion (comparative sample of the present invention) containing comparative compounds (X-1, X-2, X-3), the maximum density and minimum density In many cases, the fog exposure latitude is narrow and poor, and these are easily affected by changes in processing conditions and have poor performance.

On the other hand, the exemplary compound (I-5, I
-8, l-11) (comparative samples of the present invention), the maximum density was high and the minimum density was often low, and the fog exposure latitude was sufficiently wide to withstand fluctuations in processing conditions. There are many things that can be processed stably. For example, in Table 1, A-10 to A-14, A-17, A-1
8 has good performance.

Although gamma value data was not listed here,
Generally, a single emulsion as described above has a high gamma value and cannot provide soft gradation.

Comparative compounds and the rest 9-・mi＼ 1.・ ,・(゛で（″Table-1゛Table-2 Table-3 ☆: The additive compound was added to the core after the core was formed and immediately before the shell was formed.

Table 4 Table 5 ☆: The additive compound was added after core formation and immediately before shell formation.

Table-6 Table-7 Single emulsion A+ prepared as shown in Table-1 to Table-7
-A+a, B+~B, ll, C, ~C+q, D+~
Dos, E+ -EI9, F I-F +a
A sensitizing dye (Z-13) was added to each of G+ to cps, and a mixed emulsion was prepared by mixing a small grain emulsion and a large grain emulsion at a ratio of 25:75 as shown in Table 8゜9.10. .

Specifically, Table 8 shows emulsion C,"uc,9 with an average grain size of 0.3 μm as a small grain emulsion and emulsion El'%-Et* with an average grain size of 0.6 μm as a large grain emulsion. and are mixed as shown in the table.

Table 9 shows emulsions A3-As and Aq-A with an average grain size of 0.18 μm as small-grain emulsions, and emulsions D3-Ds and Dq-D11 with an average grain size of 0.45 μm as large-grain emulsions, respectively. The mixture shown in the table is shown.
A similar mixture is shown below. Table 10 shows emulsions C9 to C13 with an average grain size of 0.3 μm as small grain emulsions.
and emulsion E with an average grain size of 0.6 μm as a large grain emulsion,
-Etz are mixed as shown in the table, and the general formula (1
) when the amount of exemplified compound Cl-83 added is changed (same as the amount shown in Table 3 and Table 5).
A protectant containing a surfactant (S-2), dibutyl phthalate, ethyl acetate, 2,5-dioctylhydroquinone, a surfactant (S-1), and a magenta coupler (MC-1) is added to these mixed emulsions. The dispersed coupler solution was added. Gelatin is added to this, and a hardening agent (H
A-1) was added and coated on a resin-coated paper support so that the coated silver amount was 4 cm/100 CIII, and dried.

These samples were wedge exposed through a yellow filter and subjected to the same photographic processing as in processing steps [1] to [6].

For each sample after treatment, the reflection density was measured using green light. Tables 8 to 10 show the maximum density, minimum density,
The measurement results of capri exposure latitude and gamma value are shown. In Table 8, single emulsions C1 to C11, E9 to Ell
Comparison results for the cases are also shown.

Note that the gamma value is defined here as follows.

The gamma value can be expressed by the slope of the straight line connecting the density point of 20% of the maximum density and the density point of 80% of the maximum density in the characteristic curve of the sample obtained by processing with Capri exposure at 1.00 lux. can. Here, the lower the gamma value, the softer the gradation and the wider the exposure latitude.

As is clear from the results in Table 81 and Table 9, the samples according to the present invention have high maximum density, low minimum density, good image quality, and sufficiently wide performance fluctuations (light source performance fluctuations) in Capri exposure latitude. In addition, it can be processed stably against changes in the performance of processing liquids, etc.), and has a sufficiently wide and soft gradation property in terms of gamma value and a wide exposure latitude, and maintains good performance.

On the other hand, comparative samples other than those of the present invention with mixed emulsions have the same gamma value as the samples of the present invention, but many of them show deterioration in the maximum and minimum densities, especially the capri In terms of exposure latitude, all comparative samples were narrow and inferior, and were easily affected by fluctuations in processing conditions, resulting in poor performance. In addition, among the comparative samples in Table 8, those with a single emulsion have a high gamma value (generally, it is high in the case of a single emulsion), and it is difficult to obtain soft gradation like the sample according to the present invention. Can not.

Furthermore, the results in Table 10 show that the fog exposure latitude tends to become wider when more exemplified compounds of general formula (1) are used in emulsions with small average grain sizes during emulsion preparation and tempering. Table-8 Table-9 Table =10 Example-2 Table of Example-1- Emulsions C, E, prepared as shown in Table 3 and Table 5 (these are the emulsions after the formation of silver halide grains in which the exemplified compound of general formula (1) and the comparative compound were not added during emulsion preparation). Exemplary compound (1-8) of general formula (1) was added as shown in Table-11. A sensitizing dye (Z-1) was added to these and mixed at the same mixing ratio as in Tables 8 to 10 of Example 1 to prepare a mixed emulsion.

A photographic light-sensitive material was prepared as shown in Table 11 using each mixed emulsion in the same manner as in Tables 8 to 10 of Example 1, and the processing step (1) of Example 1 was carried out. ~ [6
] The same photographic processing was applied.

Table 11 shows the measurement results of maximum density, minimum density, and fog exposure latitude. Here, for convenience, samples M-2, M-3, M-6, M-7 according to the present invention from Table-10 are shown.
Insert the results of the comparison sample (single emulsion) from Table 8,
It is compared with comparative samples N-1 to N-4 prepared in Example-2.

As is clear from the results in Table 11, it can be seen that samples M-2 to M-7 according to the present invention, in which the exemplified compound of general formula [Natsu] was added during emulsion preparation adjustment, are excellent. That is, in comparative samples N-1 to N-4 in which the exemplified compound of general formula (1) was not added during emulsion preparation adjustment, the minimum density was high and the fog exposure latitude was narrow, resulting in poor performance.

＼：゛・、−ゝh−1−′ Table 11 [Effects of the Invention] As described above, according to the present invention, the maximum density is sufficiently high, the minimum density is sufficiently low, and the image quality is good, and the gamma value is sufficiently low. (Not only does it have soft gradation and a wide exposure latitude, but it also has the effect of having a sufficiently wide fog exposure latitude so that processing can be performed stably against fluctuations in processing conditions.

Claims (1)

[Scope of Claims] 1. In a direct positive silver halide photographic light-sensitive material in which a positive image is obtained directly by imparting optical fog during development or developing in the presence of a fogging agent after image exposure, a support comprising: A photographic light-sensitive layer containing at least two types of silver halide emulsions having different average grain sizes, each containing a compound represented by the following general formula [I] added at the time of preparation of the emulsion, is provided on the body.
1. A direct positive type silver halide photographic material having at least one layer. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents H or NH_2. Y is OH, NH
＿２ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼(R^
1 and R^2 each represent H, alkyl, cycloalkyl or aryl group. However, R^1 and R^2 will not become H at the same time. ) represents. [2] General formula used when preparing the emulsion with the smallest average grain size [I]
Claim 1, characterized in that the amount of the compound represented by is added is greater than the amount of the compound represented by the general formula [I] used in the preparation of other emulsions. Direct positive silver halide photographic material.